WO2011023252A4 - Ceramic membrane having a catalytic membrane-material coating - Google Patents

Ceramic membrane having a catalytic membrane-material coating Download PDF

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Publication number
WO2011023252A4
WO2011023252A4 PCT/EP2010/003094 EP2010003094W WO2011023252A4 WO 2011023252 A4 WO2011023252 A4 WO 2011023252A4 EP 2010003094 W EP2010003094 W EP 2010003094W WO 2011023252 A4 WO2011023252 A4 WO 2011023252A4
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WO
WIPO (PCT)
Prior art keywords
porous
densely sintered
sintered ceramic
ceramic membrane
membrane
Prior art date
Application number
PCT/EP2010/003094
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German (de)
French (fr)
Other versions
WO2011023252A1 (en
Inventor
Steffen Schirrmeister
Bernd Langanke
Björn HOTING
Original Assignee
Uhde Gmbh
Borsig Process Heat Exchanger Gmbh
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Publication date
Application filed by Uhde Gmbh, Borsig Process Heat Exchanger Gmbh filed Critical Uhde Gmbh
Priority to US13/393,442 priority Critical patent/US8721766B2/en
Priority to EP10727353A priority patent/EP2473252A1/en
Priority to JP2012525891A priority patent/JP2013503027A/en
Publication of WO2011023252A1 publication Critical patent/WO2011023252A1/en
Publication of WO2011023252A4 publication Critical patent/WO2011023252A4/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0048—Inorganic membrane manufacture by sol-gel transition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B01D71/0271—Perovskites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2475—Membrane reactors
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0251—Physical processing only by making use of membranes
    • C01B13/0255—Physical processing only by making use of membranes characterised by the type of membrane
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    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/2608—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead
    • C04B35/2633—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead containing barium, strontium or calcium
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/624—Sol-gel processing
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
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    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
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    • C01B2203/1241—Natural gas or methane
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/30—Hydrogen technology
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Abstract

The invention relates to a porously coated, densely sintered ceramic membrane, which can be produced from a green membrane and subsequent sintering, wherein said membrane (5) is coated with ceramic material (6), which contains noble metals, which can be produced by application and subsequent thermal treatment, wherein the noble metals are contained at a concentration of 0.2 to 5 mass percent.

Claims

GEÄNDERTE ANSPRÜCHE  CHANGED CLAIMS
beim Internationalen Büro eingegangen am  received at the International Bureau on
21. Februar 2011 (21.02.2011 )  February 21, 2011 (21/02/2011)
Ansprüche  claims
1. Porös beschichtete dicht gesinterte keramische Membran, herstellbar aus einer grünen Membran und anschließender Sinterung, wobei diese Membran mit keramischem Material beschichtet ist, das Edelmetalle enthält, herstellbar durch Aufbringung und anschließende thermische Behandlung  1. Porous coated densely sintered ceramic membrane, producible from a green membrane and subsequent sintering, said membrane is coated with ceramic material containing precious metals, producible by application and subsequent thermal treatment
dadurch gekennzeichnet,  characterized,
dass die Edelmetalle in einer Konzentration von 2,5 bis 5 Masse in der Beschichtung enthalten sind.  that the precious metals are contained in a concentration of 2.5 to 5 mass in the coating.
2. Porös beschichtete dicht gesinterte keramische Membran nach Anspruch 1, dadurch gekennzeichnet, dass die Edelmetalle in einer Konzentration von 3,8 bis 4,5 Masse % in der Beschickung enthalten sind. 2. Porous coated densely sintered ceramic membrane according to claim 1, characterized in that the noble metals are contained in a concentration of 3.8 to 4.5 mass% in the feed.
3. Porös beschichtete dicht gesinterte keramische Membran einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass die in der porösen Beschichtung enthaltenen Edelmetalle aus einer Gruppe ausgewählt werden, die Silber, Ruthenium, Platin und Palladium enthält oder dass die poröse Beschichtung eine Mischung dieser 3. Porous coated densely sintered ceramic membrane according to one of claims 1 or 2, characterized in that the precious metals contained in the porous coating are selected from a group comprising silver, ruthenium, platinum and palladium or that the porous coating is a mixture of these
Edelmetalle enthalt.  Containing precious metals.
A. Porös Beschichtete dicht gesinterte keramische Membran nach Anspruch 3, dadurch gekennzeichnet, dass die poröse Beschichtung Palladium enthält- A. Porous coated densely sintered ceramic membrane according to claim 3, characterized in that the porous coating contains palladium-
5. Porös beschichtete dicht gesinterte keramische Membran nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die poröse Beschichtung eine Schichtdicke von 3 bis 10 pm aufweist. 5. Porous coated densely sintered ceramic membrane according to one of claims 1 to 4, characterized in that the porous coating has a layer thickness of 3 to 10 pm.
6. Porös beschichtete dicht gesinterte keramische Membran nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Membran aus einer Oxidkeramik mit perowskitstruktur oder mit Brownmilleritstruktur oder mit Aurivilliusstruktur gebildet ist. 6. Porous coated densely sintered ceramic membrane according to one of claims 1 to 5, characterized in that the membrane is formed of an oxide ceramic with perowskitstruktur or with Brownmilleritstruktur or Aurivilliusstruktur.
7. Porös beschichtete dicht gesinterte keramische Membran nach Anspruch 6, dadurch gekennzeichnet, dass die Oxidkeramik vorzugsweise eine Perowskitstruktur AB03-$ aufweist, wobei A zweiwertige Kationen und B drei- oder höherwertige Kationen darstellen, der lonenradius von A größer als der lonenradius von B ist und δ eine Zahl zwischen 0,01 und 0,9, vorzugsweise zwischen 0,7 und 0,9 ist und wobei A und/oder B als Gemische unterschiedlicher Kationen vorliegen können. Porös beschichtete dicht gesinterte keramische Membran nach Anspruch 7, dadurch gekennzeichnet, dass die Kationen des Typs A ausgewählt werden aus chemischen Elementen des Periodensystems der Gruppe 2, der Gruppe 11 , der Gruppe 12 oder der Gruppe der Lanthanolden oder Mischungen dieser Kationen, vorzugsweise aus g2+, Ca2+, Sr2+, Ba2+, Cu2+, Ag2+, Zn2+, Cd2+ und/oder der Lanthanoiden und die Kationen des Typs B werden ausgewählt aus Elementen der Gruppen 3 bis 10 des Periodensystems und/oder der Lanthanoiden Gruppe, der Metalle der Gruppe 15 oder Mischungen dieser Kationen, vorzugsweise aus Fe3+, Fe4*- Ti3+, Ti4+, Zr3+, Zr4+, Ce3+, Ce4+, Mn3+, Mn4+, Co2+, Co3+, Nd3+, Nd4+, Gd3+, Gd4+, Sm8+, Sm4+, Dy3+, Dy4+, Ga3+. Yb3+, Al3+, Bi4+ oder aus Mischungen dieser Kationen. Porös beschichtete dicht gesinterte keramische Membran nach Anspruch 7, dadurch gekennzeichnet, dass die Oxidkeramik aus BaCoaFeb rc03.6 besteht, worin a + b + c = 1 bedeuten und δ eine Zahl zwischen 0,01 und 0,9, vorzugsweise zwischen 0,7 und 0,9 ist Porös beschichtete dicht gesinterte keramische Membran nach Anspruch 6, dadurch gekennzeichnet, dass die Oxidkeramik der porösen Beschickung eine andere ist, als die Oxidkeramik der dicht gesinterten keramischen Membran. Porös beschichtete dicht gesinterte keramische Membran nach Anspruch 7, dadurch gekennzeichnet, dass die Oxidkeramik der porösen BeSchichtung aus 7. Porous coated densely sintered ceramic membrane according to claim 6, characterized in that the oxide ceramic preferably has a perovskite AB0 3- $, where A is a divalent cation and B is trivalent or higher valent cations represent, the ionic radius of A is greater than the ionic radius of B and δ is a number between 0.01 and 0.9, preferably between 0.7 and 0.9 and wherein A and / or B may be present as mixtures of different cations. Porous coated densely sintered ceramic membrane according to claim 7, characterized in that the cations of type A are selected from chemical elements of the Periodic Table of Group 2, Group 11, Group 12 or the group of lanthanum or mixtures of these cations, preferably from g 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Cu 2+ , Ag 2+ , Zn 2+ , Cd 2+ and / or the lanthanides and the cations of type B are selected from elements of groups 3 to 10 of the Periodic Table and / or the lanthanoid group, metals of group 15 or mixtures of these cations, preferably from Fe 3+, Fe 4 * - Ti 3+, Ti 4+, Zr 3+, Zr 4+, Ce 3+, Ce 4+ , Mn 3+ , Mn 4+ , Co 2+ , Co 3+ , Nd 3+ , Nd 4+ , Gd 3+ , Gd 4+ , Sm 8+ , Sm 4+ , Dy 3+ , Dy 4+ , Ga 3+ . Yb 3+ , Al 3+ , Bi 4+ or mixtures of these cations. Porously coated densely sintered ceramic membrane according to claim 7, characterized in that the oxide ceramic consists of BaCo a Fe b rc0 3 .6, wherein a + b + c = 1 and δ is a number between 0.01 and 0.9, preferably between 0.7 and 0.9 is Porous coated densely sintered ceramic membrane according to claim 6, characterized in that the oxide ceramic of the porous feed is different from the oxide ceramic of the densely sintered ceramic membrane. Porously coated densely sintered ceramic membrane according to claim 7, characterized in that the oxide ceramic of the porous BeSchichtung from
BaCoaFebZr^NdOs.ö besteht, worin a + b + c + d = 1 mit d - 0,01 bis 0,5 bedeuten und Ö eine Zahl zwischen 0,01 und 0,9, vorzugsweise zwischen 0,7 und 0,9 ist und N für ein Edelmetall steht. Porös beschichtete dicht gesinterte keramische Membran nach einem der Ansprüche 1 bis 11 , dadurch gekennzeichnet, dass die Membran als Hohlfaser eingesetzt wird, die im gesinterten Zustand eine nichtlinsare, geschwungene oder gebogene BaCoaFebZr ^ N d Os.ö where a + b + c + d = 1 with d - 0.01 to 0.5 mean and Ö a number between 0.01 and 0.9, preferably between 0.7 and 0 , 9 and N is a precious metal. Porously coated densely sintered ceramic membrane according to one of claims 1 to 11, characterized in that the membrane is used as a hollow fiber, which in the sintered state, a nichtlinsare, curved or curved
Vorzugsform aufweist, wobei diese Hohlfaser mit keramischem Material porös beschichtet ist, das Edelmetalle enthält. Preferred form, said hollow fiber is coated with ceramic material porous, containing precious metals.
13. Porös beschichtete dicht gesinterte keramische Hohlfaser nach Anspruch 12, dadurch gekennzeichnet, dass die Hohlfaser einer runden Querschnittegeometrie einen Aufiendurchmesser von 0,1 mm bis 5 mm und einen Innendurchmesser von 0,01 mm bis 4,5 mm aufweist. . Herstellverfahren für porös beschichtete dicht gesinterte keramische Membranen nach einem der Ansprüche 1 bis 13 umfassend die Schritte 13. Porous coated densely sintered ceramic hollow fiber according to claim 12, characterized in that the hollow fiber of a round cross-sectional geometry has a Aufiendendurchmesser of 0.1 mm to 5 mm and an inner diameter of 0.01 mm to 4.5 mm. , A manufacturing method for porous coated densely sintered ceramic membranes according to any one of claims 1 to 13, comprising the steps
a) Lösen der Salze des keramischen Materials in Wasser und Mischen mit EDTA-Säure und Zitronensäure in einem Verhältnis von EDTA-Säure : Zitronensaure : a) dissolving the salts of the ceramic material in water and mixing with EDTA acid and citric acid in a ratio of EDTA acid: citric acid:
Metallkattonen von 1 : 1,5: 1 , wobei der pH-Wert auf 9 eingestellt wird,  Metal kattones of 1: 1.5: 1, with the pH adjusted to 9,
b) Kondensation unter Hitzezufuhr in einem Temperaturbereich von 100°C bis 200°C, wodurch ein Gel entsteht, b) condensation under heat in a temperature range of 100 ° C to 200 ° C, whereby a gel is formed,
c) thermische Behandlung des Gels bei einer Temperatur von bis zu 700°C für 1 bis 2 h, wodurch ein amorphes Pulver entsteht, c) thermal treatment of the gel at a temperature of up to 700 ° C for 1 to 2 hours, whereby an amorphous powder is formed,
d) Kalzinierung des amorphen Pulvers in einem Temperaturbereich von 800°C bis d) calcination of the amorphous powder in a temperature range of 800 ° C to
1100°C für 8 bis 10 h, bei einem kontinuierlichen Temperaturanstieg von 2°C bis 5 K/min,  1100 ° C for 8 to 10 h, with a continuous increase in temperature of 2 ° C to 5 K / min,
e) Pressen des Pulvers bei 100 bis 200 kN für 10 bis 25 min und anschließendes e) pressing the powder at 100 to 200 kN for 10 to 25 minutes and then
Extrudieren zu grünen Membranen,  Extruding to green membranes,
f) druckloses Sintern für 8 bis 16 h bei 1000°C bis 1400*0 in einer Luftatmosphäre bei einem kontinuierlichen Temperaturanstieg bzw. -abfall von 2 bis 5 K/min, wodurch eine keramische Membran entsteht, f) pressureless sintering for 8 to 16 h at 1000 ° C to 1400 * 0 in an air atmosphere with a continuous temperature increase or decrease of 2 to 5 K / min, whereby a ceramic membrane is formed,
g) Lösen eines nach den Schritten a) bis d) behandelten Edelmetall-haltigen g) dissolving a precious metal-containing material treated according to steps a) to d)
keramischen Materials in Zitronensäure mit anschließender Mahlung, wodurch eine wässrige Masse entsteht,  ceramic material in citric acid followed by grinding, whereby an aqueous mass is produced,
h) Auftragen der wässrigen Masse auf die in f) hergestellte keramische Membran, i) thermische Behandlung bei 1000°C bis 1100°C für 0,5 bis 1,5 h,  h) applying the aqueous mass to the ceramic membrane produced in f), i) thermal treatment at 1000 ° C. to 1100 ° C. for 0.5 to 1.5 h,
wobei,  in which,
die Edelmetalle der porösen BeSchichtung in einer Konzentration von 2,5 bis 5 Masse% zugemischt werden. . Membranreaktor zur selektiven Gaeabtrennung umfassend mindestens eine porös beschichtete dicht gesinterte keramische Membran nach den Ansprüchen 1 bis 13, welche den Membranreaktor in mindestens eine Permeatkammar und in mindestens eine Substratkammer aufteilt umfassend, mindestens eine Zuleitung für ein Sauerstoffenthaltendes und/oder eine Sauerstoff-abspaltende Verbindung enthaltendes the noble metals are added to the porous coating in a concentration of 2.5 to 5% by weight. , Membrane reactor for selective Gaeabtrennung comprising at least one porous coated dense sintered ceramic membrane according to claims 1 to 13, which the membrane reactor in at least one Permeatkammar and in at least a substrate chamber comprising, at least one supply line for an oxygen-containing and / or an oxygen-releasing compound containing
Speisegas, welche mit der Substratkammer verbunden ist, mindestens eine Ableitung für ein mit Sauerstoff und/oder mit mindestens einer Sauerstoff-abspaltender Feed gas, which is connected to the substrate chamber, at least one derivative for one with oxygen and / or at least one oxygen-releasing
Verbindung angereichertes Speisegas, welche mit der Substratkammer verbunden ist, gegebenenfalls mindestens einer Zuleitung für gegebenenfalls mindestens einen Reaktanden enthaltendes Spülgas, welche mit der Permeatkammer verbunden ist und mindestens eine Ableitung für Sauerstoff, Sauerstoff enthaltendes Gasgemisch und/oder oxidlerten eaktanten enthaltendes Spülgas, welche mit der Permeatkammer verbunden ist. Verwendung eines Membranreaktors nach Anspruch 15, dadurch gekennzeichnet, dass Gasbestandteile, vorzugsweise Sauerstoff, aus Gasgemischen, insbesondere aus Luft abgetrennt werden. Verwendung nach Anspruch 16, dadurch gekennzeichnet, dass der abgetrennte Sauerstoff für die anschließende Durchführung einer Oxidationsreaktion in der Gasphase eingesetzt wird. Verwendung nach Anspruch 17, dadurch gekennzeichnet, dass der abgetrennte Sauerstoff für eine partielle Oxidation eines kohlenwasserstoffhaltigen Gasgemisches zur Darstellung von Synthesegas eingesetzt wird. Verwendung nach Anspruch 17, dadurch gekennzeichnet, dass der abgetrennte Sauerstoff für eine oxidative Dehydrierung von Kohlenwasserstoffen eingesetzt wird. Verwendung nach Anspruch 17, dadurch gekennzeichnet, dass der abgetrennte Sauerstoff für eine oxidative Kupplung von Methan eingesetzt wird. Compound enriched feed gas, which is connected to the substrate chamber, optionally at least one supply line for optionally containing at least one reactant purge gas, which is connected to the permeate and at least one derivative for oxygen, oxygen-containing gas mixture and / or oxidized reactants containing purge gas, which with the Permeate chamber is connected. Use of a membrane reactor according to claim 15, characterized in that gas components, preferably oxygen, are separated from gas mixtures, in particular from air. Use according to claim 16, characterized in that the separated oxygen is used for the subsequent implementation of an oxidation reaction in the gas phase. Use according to claim 17, characterized in that the separated oxygen is used for a partial oxidation of a hydrocarbon-containing gas mixture for the preparation of synthesis gas. Use according to claim 17, characterized in that the separated oxygen is used for an oxidative dehydrogenation of hydrocarbons. Use according to claim 17, characterized in that the separated oxygen is used for an oxidative coupling of methane.
PCT/EP2010/003094 2009-08-31 2010-05-19 Ceramic membrane having a catalytic membrane-material coating WO2011023252A1 (en)

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Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2011258422C1 (en) 2010-05-24 2017-03-30 Lummus Technology Llc Nanowire catalysts
WO2012162526A2 (en) 2011-05-24 2012-11-29 Siluria Technologies, Inc. Catalysts for petrochemical catalysis
EP2785458A2 (en) 2011-11-29 2014-10-08 Siluria Technologies, Inc. Nanowire catalysts and methods for their use and preparation
AU2013207783B2 (en) 2012-01-13 2017-07-13 Lummus Technology Llc Process for providing C2 hydrocarbons via oxidative coupling of methane and for separating hydrocarbon compounds
US9446397B2 (en) 2012-02-03 2016-09-20 Siluria Technologies, Inc. Method for isolation of nanomaterials
US20140121433A1 (en) 2012-05-24 2014-05-01 Siluria Technologies, Inc. Catalytic forms and formulations
AU2013266250B2 (en) 2012-05-24 2017-07-06 Lummus Technology Llc Oxidative coupling of methane systems and methods
US9969660B2 (en) 2012-07-09 2018-05-15 Siluria Technologies, Inc. Natural gas processing and systems
CA2893948C (en) 2012-12-07 2022-12-06 Siluria Technologies, Inc. Integrated processes and systems for conversion of methane to ethylene and conversion of ethylene to higher hydrocarbon products
US9340297B2 (en) * 2013-02-19 2016-05-17 The Boeing Company Counter-flow gas separation modules and methods
US20160107143A1 (en) 2013-03-15 2016-04-21 Siluria Technologies, Inc. Catalysts for petrochemical catalysis
US10047020B2 (en) 2013-11-27 2018-08-14 Siluria Technologies, Inc. Reactors and systems for oxidative coupling of methane
CN110655437B (en) 2014-01-08 2022-09-09 鲁玛斯技术有限责任公司 System and method for ethylene to liquids
EP3097068A4 (en) 2014-01-09 2017-08-16 Siluria Technologies, Inc. Oxidative coupling of methane implementations for olefin production
US10377682B2 (en) 2014-01-09 2019-08-13 Siluria Technologies, Inc. Reactors and systems for oxidative coupling of methane
US9956544B2 (en) 2014-05-02 2018-05-01 Siluria Technologies, Inc. Heterogeneous catalysts
EP3194070B1 (en) 2014-09-17 2020-12-23 Lummus Technology LLC Catalysts for oxidative coupling of methane and oxidative dehydrogenation of ethane
US10793490B2 (en) 2015-03-17 2020-10-06 Lummus Technology Llc Oxidative coupling of methane methods and systems
US9334204B1 (en) 2015-03-17 2016-05-10 Siluria Technologies, Inc. Efficient oxidative coupling of methane processes and systems
US20160289143A1 (en) 2015-04-01 2016-10-06 Siluria Technologies, Inc. Advanced oxidative coupling of methane
US9328297B1 (en) 2015-06-16 2016-05-03 Siluria Technologies, Inc. Ethylene-to-liquids systems and methods
EP3786138A1 (en) 2015-10-16 2021-03-03 Lummus Technology LLC Oxidative coupling of methane
CA3019396A1 (en) 2016-04-13 2017-10-19 Siluria Technologies, Inc. Oxidative coupling of methane for olefin production
EP3554672A4 (en) 2016-12-19 2020-08-12 Siluria Technologies, Inc. Methods and systems for performing chemical separations
EP3630707B1 (en) 2017-05-23 2023-09-06 Lummus Technology LLC Integration of oxidative coupling of methane processes
US10836689B2 (en) 2017-07-07 2020-11-17 Lummus Technology Llc Systems and methods for the oxidative coupling of methane
CN111224110A (en) * 2018-11-27 2020-06-02 中国科学院大连化学物理研究所 Proton type solid oxide fuel cell cathode material and application thereof
CN115228284B (en) * 2022-06-16 2023-11-21 江苏京源环保股份有限公司 Ceramic membrane filtration equipment for high-temperature flue gas waste heat collection and dust removal catalysis

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4791079A (en) 1986-06-09 1988-12-13 Arco Chemical Company Ceramic membrane for hydrocarbon conversion
NO304808B1 (en) 1989-05-25 1999-02-15 Standard Oil Co Ohio Fixed multicomponent membrane, method of milling such a membrane and use thereof
US5498278A (en) * 1990-08-10 1996-03-12 Bend Research, Inc. Composite hydrogen separation element and module
US5645626A (en) * 1990-08-10 1997-07-08 Bend Research, Inc. Composite hydrogen separation element and module
US6033632A (en) 1993-12-08 2000-03-07 Eltron Research, Inc. Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them
US6355093B1 (en) 1993-12-08 2002-03-12 Eltron Research, Inc Two component-three dimensional catalysis
US5534471A (en) * 1994-01-12 1996-07-09 Air Products And Chemicals, Inc. Ion transport membranes with catalyzed mixed conducting porous layer
US5820655A (en) 1997-04-29 1998-10-13 Praxair Technology, Inc. Solid Electrolyte ionic conductor reactor design
US6010614A (en) * 1998-06-03 2000-01-04 Praxair Technology, Inc. Temperature control in a ceramic membrane reactor
JP3855799B2 (en) * 2001-02-27 2006-12-13 Ｊｆｅスチール株式会社 Mixed conductive oxygen separation membrane having catalyst layer on membrane surface and method for producing oxygen using the same
JP4430291B2 (en) * 2001-10-15 2010-03-10 国際石油開発帝石株式会社 Syngas production method
EP1452505A4 (en) 2001-10-15 2006-03-29 Nippon Steel Corp Porcelain composition, composite material comprising catalyst and ceramic, film reactor, method for producing synthetic gas, apparatus for producing synthetic gas and method for activating catalyst
EP1487563A4 (en) * 2002-03-05 2005-07-20 Eltron Research Inc Hydrogen transport membranes
EP2527046A1 (en) * 2003-07-29 2012-11-28 Intelligent Energy, Inc. Thin hydrogen separation membrane
KR100679341B1 (en) * 2004-09-15 2007-02-07 한국에너지기술연구원 Preparation Method of Palladium Alloy Composite Membrane for Hydrogen Separation
DE102005005464B4 (en) * 2005-02-04 2007-06-14 Uhde Gmbh Composites of ceramic hollow fibers, process for their preparation and their use
DE102005006571A1 (en) * 2005-02-11 2006-08-17 Uhde Gmbh Process for oxygen enrichment in gases, suitable plants and their use
US8807350B2 (en) * 2005-07-14 2014-08-19 Ben-Gurion University Of The Negev Research & Development Authority Composite membranes and methods for their preparation
EP1847311A1 (en) 2006-04-19 2007-10-24 Universität Hannover Composite Membrane
DE102006060171A1 (en) 2006-12-18 2008-06-26 Alphacool Gmbh Cooling device for cooling microelectronic component, particularly processor cooling device, comprises base plate, which is provided for thermal contact of microelectronic component with contact surface

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